Homochiral metal-organic macrocyclic complexes are of great significance owing to their chirality and well-defined internal cavities that potentially have the ability to mimic complicated biological processes. Here we report a novel metal/anion-coordination co-driven strategy for the formation of nanoscale supramolecular metallocycles with unique topology, large size, and desired chirality. The enantiomeric Janus-type metallocyclic strips are assembled based on the synergistic coordination of sulfate anions and Co ions to a bifunctional achiral ligand combining the -phenylene-(bis)urea anion-chelating and 8-hydroxyquinoline metal-coordinating sites. The inherent chirality arises from two types of helical chiralities (triply twisted Möbius ring and circular helicate), which is observed for the first time for metal-organic complex systems. Notably, spontaneous chiral resolution by conglomerate crystallization into a pair of enantiomers ( or ) is realized, which is attributed to the multiple weak intermolecular interactions facilitating the hierarchically helical superstructure.
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http://dx.doi.org/10.1021/jacs.3c05746 | DOI Listing |
J Am Chem Soc
August 2023
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, China.
Homochiral metal-organic macrocyclic complexes are of great significance owing to their chirality and well-defined internal cavities that potentially have the ability to mimic complicated biological processes. Here we report a novel metal/anion-coordination co-driven strategy for the formation of nanoscale supramolecular metallocycles with unique topology, large size, and desired chirality. The enantiomeric Janus-type metallocyclic strips are assembled based on the synergistic coordination of sulfate anions and Co ions to a bifunctional achiral ligand combining the -phenylene-(bis)urea anion-chelating and 8-hydroxyquinoline metal-coordinating sites.
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